N-carbonyl-N-(2-furfuryl)-4-haloanilines and herbicidal use thereof

ABSTRACT

A compound having the following structural formula ##STR1## wherein R is nitro or hydrogen; R 1  is C 1  -C 4  alkyl or C 1  -C 3  alkylthio; and R 2  is hydrogen or chlorine and X is chlorine, bromine, or iodine.

BACKGROUND OF THE INVENTION

The present invention relates to certain aniline compounds which are especially useful as post-emergent herbicides against annual and perennial grasses and broadleaf weeds. The compounds are especially useful in controlling weeds in rice, paddy water, post-emergent and post-flood.

Hericides are widely used by farmers, commercial agricultural companies, and other industries in order to increase crop yields for such staple crops as corn, soybeans, rice, and the like, and to eliminate weed growth along highways, railroad rights-of-way, and other areas. Herbicides are effective in killing or controlling vegetation which compete for soil nutrients with the crop plants, and by reason of the fact that they control undesired vegetation.

There are a number of different types of herbicides presently sold commercially, and these fall into two general categories. These categories are pre-emergence and post-emergence herbicides. The pre-emergence herbicides are normally incoporated into or applied to the soil prior to the emergence of the undesired vegetation and the post-emergence herbicides are normally applied to the undesirable vegetation or to the soil surface where it is growing.

DESCRIPTION OF THE INVENTION

This invention relates to N-carbonyl-N-(2-furfuryl)-4-halo-chloroanilines as post-emergent herbicides. The novel compounds of this invention have the following structural formula ##STR2## wherein R is nitro or hydrogen, preferably nitro; R¹ is C₁ -C₄ alkyl, preferably cyclopropyl or ethyl, or C₁ -C₃ alkylthio, preferably methylthio and most preferably cyclopropyl; and R² is hydrogen or chlorine and X is chlorine, bromine or iodine, preferably chlorine or bromine.

In the above description of the compounds of this invention alkyl includes both straight, branched and cyclic configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and cyclopropyl.

The compounds of this invention are active post-emergent herbicides. They are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

The compounds of the present invention can be prepared by the following general method. ##STR3## where R, R¹, R² and X are as defined.

In general for step (1) the aniline reaction product is prepared by reacting equal mole amounts of the 5-substituted furfuraldehyde with the 4-chloroaniline to form an imine which is then reduced with sodium borohydride to give the desired intermediate.

In step (2) the aniline intermediate is reacted with an equal mole amount of the substituted carboxylic acid chloride. Preferably, the reaction is run in a solvent in the presence of an acid chloride acceptor such as triethylamine.

The desired product is recovered by conventional techniques.

The following example teaches the synthesis of a representative compound of this invention.

EXAMPLE I N-2-Furfuryl-4,4-chloroaniline ##STR4##

Ten grams (10 g, 0.104 mole) of furfurylaldehyde was dissolved in 250 milliliters (ml) methanol. The 4-chloroaniline (13.g, 0.104 mole) was added. A precipitate formed after the solution was heated to 40° C. for 10 minutes. The mixture was refluxed for one hour, then 3.0 g (20% equimole excess) of NaBH₄ was added in small portions to the cooled suspension. The precipitate redissolved. The solution was warmed to 40° C. for 10 minutes. The solution was cooled and poured into 250 ml of water containing 6.0 g NaOH. A oil formed extraced with methylene chloride. The extracts were dired and the solvent removed to yield a solid which was triturated in hexane and ether to yield the desired product.

EXAMPLE II N-(cyclopropane carbonyl)-N-2-furfuryl-4-chloroaniline ##STR5##

2.5 grams (0.011 mole) of N-2-furfuryl-4-chloroaniline, 1.1 g (0.011 mole) triethylamine and 50 ml tetrahydrofuran were combined in a 100 ml, 3-necked reaction flask equipped with a magnetic stirrer, thermometer, and condenser. While stirring the resulting solution 1.3 g (0.012 mole, 1.1 ml) cyclopropane carboxylic acid chloride was added from a syringe. The resulting reaction was exothermic and produced a white precipitate. The mixture was stirred at room temperature for 30 minutes and refluxed for about 1 hour and cooled. The formed triethylamine hydrochloride was separated by filtration. The filtrate was vacuum stripped to yield 3.6 g of the desired product, a dark brown oil.

The following is a table of certain selected compounds that are preparable according to the procedure described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                  TABLE I                                                          ______________________________________                                          ##STR6##                                                                      Compound                                                                       Number   R      R.sup.1   R.sup.2                                                                            X     m.p. °C.                            ______________________________________                                         .sup. 1.sup.a                                                                           H                                                                                      ##STR7## H   Cl    dark brown liquid                          2        H      C.sub.2 H.sub.5                                                                          H   Cl    dark brown liquid                          3        H      CH.sub.3 S                                                                               H   Cl    dark brown liquid                          4        H                                                                                      ##STR8## Cl  Cl    dark brown liquid                          5        H      t-C.sub.4 H.sub.9                                                                        Cl  Cl    dark brown liquid                          6        NO.sub.2                                                                               ##STR9## Cl  Br    114-116                                    7        NO.sub.2                                                                              C.sub.2 H.sub.5                                                                          Cl  Br    114-118                                    ______________________________________                                          .sup.a prepared in Example II.                                           

HERBICIDAL SCREENING TESTS

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Post-emergence herbicide test.

On the day preceding treatment, seeds of eight different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea), curly dock (CD) (Rumex crispus), and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha) 10-12 days after seed planting. The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling the soil surface and not the foliate of the sprouted plants. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Table II.

                  TABLE II                                                         ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNG                             ______________________________________                                         1      65     55     10   95    100  95   100  35                              2      35     20      0    0    20   30   90   0                               3      95     65      0   20    55   45   40   0                               4      70     75     60   95    75   100  60   0                               5       0      0      0   20     0   100   0   0                               6      100    85     30   95    10   100  98   0                               7      20     20     20   --     0   10   25   0                               ______________________________________                                          -- Indicates species did not germinate.                                  

The compounds of the present invention are useful as herbicides, especially as post-emergence herbicides, and can be applied in a variety of ways at various concentrations. In practice, the compounds herein defined are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds may be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. Preferred formulations for pre-emergence herbicidal applications are wettable powders, emulsifiable concentrates and granules. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.05 to approximately 25 pounds per acre, preferably from about 0.1 to about 10 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphtha, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, bentonite clays, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 5% to about 25% of active ingredients which may include surface-active agents such as wetting agents, dispersing agents or emulsifiers; oil such as heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydroxy alcohols; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 15% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phototoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers and other herbicides, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the abovedescribed compounds include, for example, 2,4-dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof, triazine derivatives, such as 2,4-bis(3-methoxypropylamino)-6-methylthio-s-triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, and 2-ethylamino-4-isopropyl-amino-6-methyl-mercapto-s-triazine; urea derivatives, such as 3-(3,5-dichlorophenyl)-1,1-dimethylurea and 3-(p-chlorophenyl)-1,1-dimethylurea; and acetamides such as N,N-diallyl-α-chloroacetamide, and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic acid; thiocarbamates such as S-propyl N,N-dipropylthiocarbamate, S-ethyl N,N-dipropylthiocarbamate, S-ethyl cyclohexylethylthiocarbamate, S-ethyl hexahydro-1H-azepine-1-carbothioate and the like; anilines such as 4-(methylsulfonyl)-2,6-dinitro-N,N-substituted aniline, 4-trifluoromethyl-2,6-dinitro-N,N-di-n-propyl aniline, 4-trifluoromethyl-2,6-dinitro-N-ethyl-N-butyl aniline, 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoic acid, 2-[1-(ethoxyimino)butyl]-5-[2-ethylthio)propyl]-3-hydroxy-2-cyclohexene-1-one, (±)-butyl- 2-[4-[(5-trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanate, sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, 3-isopropyl-1H-2,1,3-benzothiadiazine-4(3H)-one-2,2-dioxide, and 4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5(4H)-one or (4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one). Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand, and the like. 

We claim:
 1. A compound having the structural formula ##STR10## wherein R is nitro or hydrogen; R¹ is C₁ -C₄ alkyl, C₁ -C₃ alkylthio, or cyclopropyl; and R² is hydrogen or chlorine and X is chlorine, bromine, or iodine.
 2. The compound of claim 1 wherein R is nitro or hydrogen, R¹ is methylthio, cyclopropyl or ethyl, R² is hydrogen or chlorine and X is chlorine or bromine.
 3. The compound of claim 2 wherein R is hydrogen, R¹ is cyclopropyl, R² is hydrogen and X is chlorine.
 4. The compound of claim 2 wherein R is hydrogen, R¹ is cyclopropyl, R² is chlorine and X is bromine.
 5. The compound of claim 2 wherein R is nitro, R¹ is cyclopropyl, R² is chlorine and X is bromine.
 6. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound having the formula ##STR11## wherein R is nitro or hydrogen; R¹ is C₁ -C₄ alkyl, C₁ -C₃ alkylthio, or cyclopropyl; and R² is hydrogen or chlorine and X is chlorine, bromine, or iodine.
 7. The method of claim 6 wherein R is nitro or hydrogen, R¹ is methylthio, cyclopropyl or ethyl, R² is hydrogen or chlorine and X is chlorine or bromine.
 8. The method of claim 7 wherein R is hydrogen, R¹ is cyclopropyl, R² is hydrogen and X is chlorine.
 9. The method of claim 7 wherein R is hydrogen, R¹ is cyclopropyl, R² is chlorine and X is bromine.
 10. The method of claim 7 wherein R is nitro, R¹ is cyclopropyl, R² is chlorine and X is bromine. 